KR20070118597A - Coating composition and coated article - Google Patents

Abstract

Disclosed is a coating composition which enables form a coating film that can maintain low refractive index, high abrasion resistance, high antifouling property, high chemical resistance and high crack resistance even when it is formed on a plastic base material such as bases made of plastics and exposed to high temperatures during or after the coating film formation. Specifically disclosed is a coating composition containing a silane compound represented by the general formula (A) below and an epoxy group-containing organic compound which has one or more epoxy groups in a molecule, wherein the silane compound content is 60-97% by weight relative to the total amount of resin components and the epoxy group-containing organic compound content is 3-10% by weight relative to the total amount of resin components. XmR13-mSi-Y-SiR13-mXm (A) [In the formula, R1 represents a monovalent hydrocarbon group having 1-6 carbon atoms; Y represents a divalent organic group having one or more fluorine atoms; X represents a hydrolyzable group; and m represents an integer of 1-3.] A coating film made of such a coating composition is able to maintain high crack resistance even when it is exposed to high temperatures.

Description

Coating material composition and paints {COATING COMPOSITION AND COATED ARTICLE}

The present invention relates to a coating material composition having a low refractive index and capable of realizing high scratch resistance, antifouling property, chemical resistance, and crack resistance, and a coated article formed with the cured coating film.

Conventionally, chemically strong fluorine resin has been mainly used as a coating material composition for the use which requires chemical resistance. Moreover, the low refractive index which a fluororesin has essentially is utilized, and it is applied also to antireflection use, such as a display. In addition, the fluorine resin has been applied as a rubber or a coating agent, but it has been difficult to make a hard protective coating excellent in scratch resistance because of its molecular structure.

In addition, in recent years, hydrolyzable silane compounds having a perfluoroalkyl group have been developed, and various coating agents such as water repellency, oil repellency, antifouling property, antireflection, etc. have been developed utilizing their properties. However, since the perfluoroalkyl group having such a characteristic is bulky and inert, the crosslinking density of the cured film is low, and as a result, even if it is quite hard compared with the fluorine resin, scratch resistance is still insufficient.

Moreover, the following things are developed for the purpose of improving scratch resistance.

First, (1) As disclosed in Japanese Patent Laid-Open No. 2002-53805, it is a method of cohydrolyzing various silane compounds such as perfluoroalkyl group-containing silane and tetraalkoxysilane.

Moreover, as disclosed in (2) JP-A-6-29332, a disilane compound containing perfluoroalkylene as a spacer in a perfluoroalkyl group-containing silane and tetraalkoxysilane are used together. System.

In addition, as disclosed in (3) Japanese Patent No. 2629813, a system using a disilane compound containing a perfluoroalkylene as a spacer and an epoxy functional silane is proposed.

By these techniques, the target antifouling property, scratch resistance, adhesiveness, and antireflection property were able to ensure the comparatively favorable level. However, since the fluorine content is lowered, there is a problem in practical use due to the lack of chemical resistance, particularly alkali resistance, which is a weak point of the polysiloxane system, which is inherently good for drugs such as household detergents.

Moreover, in the composition disclosed by Unexamined-Japanese-Patent No. 2004-315712, a higher level of chemical resistance is achieved by containing the disilane compound which has a specific structure, or its (partial) hydrolyzate. However, there is a problem that cracks are likely to occur when high heat is applied in film formation or other processes, or when high heat is applied after film formation. Particularly, when a film is formed on a plastic substrate such as plastic, There was a problem that the occurrence of the same crack was remarkable.

Disclosure of the Invention

The present invention has been made in view of the above-mentioned point, and even when a film is formed on a plastic substrate such as a plastic substrate, the film has a low refractive index, high scratch resistance, antifouling resistance, and resistance against corrosion when exposed to high temperature after film formation or after film formation. An object of the present invention is to provide a coating material composition capable of maintaining chemical resistance and crack resistance, and a coating product having a coating film formed from the coating material composition.

The coating material composition by this invention contains the silane compound represented by the following general formula (A), and the epoxy group containing organic compound containing 1 or more epoxy groups in a molecule | numerator, and content of the said silane compound is with respect to resin component whole quantity. It is 60 to 97 weight%, and content of the said epoxy group containing organic compound is 3 to 10 weight% with respect to the resin component whole quantity, It is characterized by the above-mentioned.

[R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is a divalent organic group containing one or more fluorine atoms. X is a hydrolyzable group. m is an integer of 1 to 3.]

The film formed from such a coating material composition can be maintained even when high crack resistance is exposed under high temperature.

It is preferable that the said epoxy group containing organic compound contains the compound represented by the following general formula (B), and at least 1 sort (s) of compound chosen from the compound represented by the following general formula (C).

[R <^2> , R <^3> is a C1-C16 organic group and at least one contains an epoxy group. Z is a hydrolyzable group. n and p are integers of 0 to 2 and 1 ≦ n + p ≦ 3.]

[Formula 1]

[R ⁴ to R ¹⁵ are organic groups, and at least one of them contains an epoxy group. q, r, s, t are integers from 0 to 12.]

Moreover, it is preferable that the said epoxy group containing organic compound contains 2 or more epoxy groups in a molecule | numerator.

Moreover, it is preferable that the said coating material composition contains the alkyl fluoride-containing alkoxysilane represented by the following general formula (D).

[R _f is a monovalent organic group containing one or more fluorine atoms. X is a hydrolyzable group.]

In addition, the coating composition preferably contains a filler.

Moreover, it is preferable that content of the said epoxy group containing organic compound is 3 to 10 weight% with respect to the silane compound represented by the said General formula (A).

The coated article according to the present invention is formed by forming a cured coating film of the above coating material composition on the surface of a base material.

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated.

The coating material composition which concerns on this invention contains as an essential component the silane compound represented by the following general formula (A), and the epoxy group containing organic compound containing one or more epoxy groups in a molecule | numerator.

[R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is a divalent organic device containing at least one fluorine atom. X is a hydrolyzable group. m is an integer of 1 to 3.]

Y in Formula (A) is a divalent organic group having one or more fluorine atoms, but the number of fluorine atoms is preferably 4 to 50, particularly preferably 8 to 24. In particular, in order to express various functions, such as antireflection, antifouling property, and water repellency, on a good standard, it is preferable to contain a large amount of fluorine atoms. In addition, since a perfluoroalkylene group is rigid, it is preferable to contain as much fluorine atoms as possible in order to obtain a film with high hardness and abrasion resistance. If the fluorine atom is contained in a large amount, the chemical resistance is also improved. Therefore, as Y, it is preferable that it is the following structure.

[n is an integer from 2 to 20]

As n in the said structure, it is necessary to satisfy the value of 2-20, More preferably, it is 4-12, Especially preferably, it is good to satisfy the range of 4-10. When less than this, various functions, such as antireflection property, antifouling property, and water repellency, and chemical-resistance may not be fully acquired, and when too much, sufficient crosslinking density may fall and sufficient scratch resistance may not be obtained.

Although R <^1> represents a C1-C6 monovalent hydrocarbon group, specifically, alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, a phenyl group, etc. can be illustrated. In order to acquire favorable scratch resistance, a methyl group is preferable.

Although m is an integer of 1-3, Preferably it is set to 2 or 3. In order to make especially a highly hard film, it is preferable to set it as m = 3.

X represents a hydrolyzable group. Specific examples include, halogen atoms, OR _x (R _x is a monovalent group having 1 to 6 carbon atoms hydrocarbon group) in time by Organo nook represented by, in particular methoxy, ethoxy, propoxy, iso-propoxy group, such as Cl, Alkoxy groups, such as an alkoxy group, such as a butoxy group, an alkenoxy group, such as an isopropenoxy group, an acyloxy group, such as an acetoxy group, a ketoxime group, such as methyl ethyl ketoxim group, an alkoxyalkoxy group, such as a methoxyethoxy group, etc. are mentioned. . Among these, an alkoxy group is preferable, and in particular, a silane compound of a methoxy group and an ethoxy group is preferable because it is easy to handle and the control of the reaction during hydrolysis is also easy.

As a specific example of the silane compound represented by such a general formula (A), the following are mentioned, for example.

[Formula 2]

The silane compound represented by the said General formula (A) is contained in the range of 60-97 weight% with respect to resin component whole quantity, Preferably it is 65-85 weight% in a coating material composition. For this reason, the chemical-resistance of the film by the silane compound represented by General formula (A) can be improved, and the alkali resistance which was a problem of the conventional polysiloxane film can be aimed at.

As the epoxy group-containing organic compound containing at least one epoxy group in the molecule, a suitable one can be used. In particular, it is preferable to use two or more epoxy groups in the molecule, and in this case, the chemical resistance of the film can be further improved. It can be. The epoxy group containing organic compound containing two or more epoxy groups in such a molecule | numerator is contained in 3 to 10 weight% with respect to the resin component whole quantity. If it is less than 3% by weight, the crack resistance of the film cannot be sufficiently improved, and if it is more than 10% by weight, the chemical resistance of the film cannot be sufficiently improved, and the wear resistance of the film may be deteriorated.

As this epoxy group containing organic compound, Preferably, what is chosen from the compound represented by the following general formula (B) and the compound represented by the following general formula (C) is used, One or more types can be used from such a compound. Can be. In this case, the crack resistance can be further improved without lowering the chemical resistance and the wear resistance of the film. It is preferable that content of the sum total of this epoxy group containing organic compound is 3 to 10 weight% with respect to resin component whole quantity, and when this content is too small, there exists a possibility that it may not fully improve crack resistance, When content is excess, there exists a possibility that chemical resistance and abrasion resistance may fall.

[R <^2> , R <^3> is a C1-C16 organic group and at least one contains an epoxy group. Z is a hydrolyzable group. n and p are integers of 0 to 2 and 1 ≦ n + p ≦ 3.]

[Formula 3]

[R ⁴ to R ¹⁵ are organic groups, and at least one of them contains an epoxy group. q, r, s, t are integers from 0 to 12.]

As a compound represented by the said General formula (B), it selects suitably according to the objectives, such as adhesiveness to a base material, the hardness and low reflectance of the coating film obtained, the life of a composition, etc. For example, glycidoxy methyl trimethoxy silane, glycidoxy methyl triethoxy silane, (alpha)-glycidoxy ethyl trimethoxysilane, (alpha)-glycidoxy ethyl triethoxysilane, (beta)-glycidoxy ethyl Triethoxysilane, β-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, δ- ( 3, 4- epoxycyclohexyl) butyl triethoxysilane etc. are mentioned.

Moreover, as a compound represented by the said General formula (C), R <^4> -R <^15> in formula represents organic groups, such as suitable hydrocarbon groups, such as a methyl group. In addition, at least one of these R <^4> -R <^15> contains an epoxy group, for example, what has the following structure is mentioned.

[Formula 4]

As a specific example of the compound represented by said general formula (C), what is shown below is mentioned, for example.

[Formula 5]

[Formula 6]

Moreover, as an epoxy group containing organic compound, you may use a suitable epoxy compound other than what was shown to the said general formula (B) (C). As such an epoxy compound, what is shown below is mentioned, for example.

[Formula 7]

Although content of an epoxy group containing organic compound is adjusted suitably, Preferably it is made into the range of 3 to 10 weight% with respect to the silane compound represented by the said General formula (A), and to reduce the chemical-resistance and abrasion resistance of a film Without work, crack resistance can be further improved. When this content is too small than the said range, it will become difficult to fully improve crack resistance, and when it exceeds this range, there exists a possibility that chemical resistance and abrasion resistance may fall.

Moreover, in a coating material composition, you can also contain the alkyl fluoride-containing alkoxysilane represented by the following general formula (D).

[R _f is a monovalent organic group containing at least one fluorine atom. X is a hydrolyzable group.]

By containing such a thing, the refractive index of the film formed can further be reduced.

In the general formula (D), the number of fluorine atoms in R _f is preferably 3 to 25, particularly 3 to 17. inter alia,

Is preferable because it does not contain a polar moiety.

In addition, X which is a hydrolysable group can be the same as what is in the said general formula (A).

As a fluorinated alkyl group containing alkoxysilane represented by such general formula (D), what is shown below is mentioned, for example.

Although content of the alkyl fluoride-containing alkoxysilane represented by this general formula (D) and its hydrolyzate (partially hydrolyzate) is adjusted suitably, when the addition amount increases, the scratch resistance of a film falls, so that the total amount of the resin component in a composition It is preferable to set it as the range of 1-30 weight% with respect to, and 1-10 weight% is especially preferable.

In addition, as a coating composition, silica, aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, tin oxide, indium oxide as a filler for the purpose of adjusting physical properties, such as hardness, abrasion resistance, electroconductivity of a film, Inorganic oxide fine particles, such as these complex oxides, and these hollow sol may be mix | blended. In particular, when the film is to be kept at a low refractive index, it is preferable to use colloidal silica and a hollow silica sol. It is preferable that the average primary particle diameter of a suitable inorganic fine particle is 0.001-0.1 micrometer, More preferably, it becomes 0.001-0.05 micrometer. When average primary particle diameter exceeds 0.1 micrometer, there exists a tendency for transparency of the cured film formed with the composition to be prepared to fall. These inorganic oxide fine particles may use those obtained by treating the surfaces with organometallic compounds such as silane, titanium, aluminum, or zirconium coupling agents.

Moreover, as a filler, you may mix | blend the hollow microparticles | fine-particles whose outer shell was formed from the metal oxide. As such hollow fine particles, hollow silica fine particles can be used. The hollow silica fine particles have a cavity formed in the inside of the outer shell, and are not particularly limited as long as they are such, but specifically, the following may be used. For example, hollow silica fine particles having a cavity inside an outer shell (cell) made of a silica-based inorganic oxide can be used. The silica-based inorganic oxide includes (A) a single layer of silica, (B) a single layer of a composite oxide composed of inorganic oxides other than silica and silica, and (C) a double layer of (A) and (B) layers. Say that. The outer shell may be porous having pores, or the pores may be blocked by the operation described later to seal the cavity. It is preferable that an outer shell is a some silica type coating layer which consists of an inner 1st silica coating layer and an outer 2nd silica coating layer. By providing a 2nd silica coating layer outside, the hollow microparticles | fine-particles which closed the micropore of an outer shell and densified an outer shell or sealed the cavity inside the outer shell can be obtained.

It is preferable that the thickness of a 1st silica coating layer shall be 1-50 nm, especially the range of 5-20 nm. If the thickness of the first silica coating layer is less than 1 nm, it becomes difficult to maintain the particle shape, there is a fear that hollow silica fine particles cannot be obtained, and when forming the second silica coating layer, the partial hydrolyzate of the organosilicon compound is There exists a possibility that it may become difficult to remove a nuclear particle component by entering a pore of a nuclear particle. On the contrary, when the thickness of the first silica coating layer exceeds 50 nm, there is a fear that the proportion of the cavities in the hollow silica fine particles decreases and the decrease in the refractive index becomes insufficient. In addition, it is preferable that the thickness of an outer shell exists in the range of 1 / 50-1 / 5 of an average particle diameter. The thickness of the second silica coating layer may be such that the total thickness of the first silica coating layer is in the range of 1 to 50 nm, preferably in the range of 20 to 49 nm as long as the outer shell is densified.

At least any one of the solvent used when preparing hollow silica microparticles | fine-particles, and the gas which permeates at the time of drying exists in a cavity. In addition, the precursor material for forming a cavity may remain in the cavity. The precursor substance adheres to the outer shell and remains slightly, and occupies most of the cavity. Here, the precursor material is a porous material remaining after removing a part of its constituents from the nuclear particles for forming the first silica coating layer. As the nucleus particles, porous composite oxide particles composed of silica and inorganic oxides other than silica are used. As the inorganic oxide, at least, such as _{Al 2 O 3, B 2 O} 3, TiO 2, ZrO 2, SnO 2, Ce 2 O 3, P 2 O 5, Sb 2 O 3, MoO 3, ZnO 2, WO 3 Or 2 or more types can be mentioned. TiO ₂ -Al ₂ O ₃ , TiO ₂ -ZrO ₂ , and the like can be exemplified as two or more kinds of inorganic oxides. The solvent or gas also exists in the pores of the porous material. When the amount of removal of the constituent components at this time increases, hollow silica fine particles are obtained in which the void volume increases and the refractive index decreases. The transparent coating obtained by blending the hollow silica fine particles has a low refractive index and is excellent in antireflection performance.

The coating material composition which concerns on this invention can be prepared by mix | blending said matrix formation material and hollow fine particles. In the coating material composition, the weight ratio between the hollow fine particles and the other components is not particularly limited, but it is preferable to set so as to be in the range of hollow fine particles / other components (solid content) = 80/20 to 10/90, More preferably, it is 50 / 50-15 / 85. When there are more hollow microparticles | fine-particles, there exists a possibility that the mechanical strength of the cured film obtained by a coating material composition may fall, On the contrary, when there are few hollow microparticles | fine-particles, there exists a possibility that the effect of expressing the low refractive index of a cured film may become small.

In addition, silica particles in which the inside of an outer shell is not a cavity can be added to a coating material composition. By mix | blending this silica particle, the mechanical strength of the hardened film formed by a coating material composition can be improved, and surface smoothness and crack resistance can also be improved. The form of the silica particles is not particularly limited, and may be, for example, a powder form or a sol form. When the silica particles are used in the form of a sol, that is, colloidal silica, a hydrophilic organic solvent dispersible colloidal such as, for example, water dispersible colloidal silica or alcohol can be used. Generally, such colloidal silica contains 20 to 50 weight% of silica as solid content, and a silica compounding quantity can be determined from this value. It is preferable that the addition amount of this silica particle is 0.1-30 weight% with respect to solid content whole quantity in a coating material composition. If it is less than 0.1 weight%, the effect by the addition of this silica particle may not be acquired, and if it exceeds 30 weight% on the contrary, there exists a possibility that it may have an adverse effect, such as raising the refractive index of a cured film.

As mentioned above, when a filler is contained, the improvement of abrasion resistance of a coating film can be anticipated further, and when a low refractive index filler, such as magnesium fluoride and hollow particle which are especially low refractive index, is added, it can be expected to further reduce refractive index. have.

Moreover, as another organosilicon compound which can be used together other than the said component, the dialkyl siloxy type hydrolyzable organosilane represented by the following general formula is mentioned.

[Formula 8]

[R ¹ , R ² , R are alkyl groups, m is an integer of 1 to 3, n is an integer of 2 to 200]

As such a dialkyl siloxy type hydrolyzable organosilane, the thing of the structure shown below is mentioned, for example.

[Formula 9]

As other organosilicon compounds, silicates such as tetraethoxysilane, alkylsilanes such as methyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, phenyltrimethoxysilane, etc. And various compounds such as silane coupling agents such as phenylsilanes, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ-melcaptopropyltrimethoxysilane.

It is preferable to make these organosilicon compounds into 30 weight% or less with respect to resin component whole quantity. When this content is excessive, crack resistance of a film may fall or hydrophilicity may become high and chemical resistance may fall.

The compound shown in Formula (A), (B), (D) mentioned above, or the said other organosilicon compound which can be used together may be used as it is, in the form of (partial) hydrolysis, or in the form hydrolyzed in the following solvent You may also use. In particular, from the viewpoint of increasing the curing rate after coating, a method of using in the form of (partly) hydrolysis is preferable. In the case of hydrolysis, it is preferable that the molar ratio of water involved in the hydrolysis relative to the hydrolyzable group is in the range of 0.1 to 10,

Conventionally well-known methods can be used for hydrolysis, As this hydrolysis catalyst or a catalyst for hydrolysis-condensation hardening, Acids, such as hydrochloric acid, an acetic acid, a maleic acid, sodium hydroxide (NaOH), ammonia, triethylamine, di Amine compounds such as butylamine, hexylamine, octylamine, dibutylamine, salts of amine compounds, bases such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, potassium fluoride and sodium fluoride Organic carboxyls such as fluorinated salts, solid acidic catalysts or solid basic catalysts (e.g., ion-exchange resin catalysts), iron-2-ethylhexate, titanium naphate, zinc stearate, dibutyltin diacetate Metal salts of acids, tetrabutoxytitanium, tetra-i-propoxytitanium, dibutoxy- (bis-2,4-pentanedionate) titanium, di-i-propoxy (bis-2,4-pentanedionate) Organic titanium esters such as titanium Tetrabutoxy zirconium, tetra-i-propoxy zirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di-i-propoxy (bis-2,4-pentanedionate) zirconium Organometallic compounds such as alkoxyaluminum compounds such as organic zirconium esters and aluminum triisopropoxide, aluminum chelate compounds such as aluminum acetylacetonate complexes, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltriethoxysilane, Amino alkyl substituted alkoxysilanes such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) -γ-aminopropyltriethoxysilane are exemplified, and these alone or You may mix and use.

The addition amount of such a catalyst is 0.01-10 weight part, Preferably it is 0.1-1 weight part with respect to 100 weight part of compounds which should be (partial) hydrolyzed. When this amount is less than 0.01 part by weight, it may take too long to complete the reaction or the reaction may not proceed. Moreover, when it exceeds 10 weight part, it is disadvantageous in terms of cost, and the composition or hardened | cured material obtained may color, or a side reaction may increase.

In addition, this composition can be diluted and used with a solvent. Examples of the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol and diacetone alcohol, ethylene glycol monomethyl ether and ethylene glycol Glycol ethers such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, esters such as ethyl acetate, butyl acetate and ethyl acetoacetate And xylene, toluene and the like. Although the addition amount of a solvent is arbitrary, when the ease of coating, the control of coating film thickness, and stability of a coating composition are considered, it is preferable that content of the solvent in a composition is 50-99 weight%, Especially preferably, it is 70-98 % By weight.

And the coating material composition prepared as mentioned above is apply | coated to the surface of a base material, and a coating is formed, and this coating is dried and hardened | cured, and the coated article in which the cured film which has a low refractive index is formed in the surface can be obtained. The substrate on which the coating material composition is coated is not particularly limited, and examples thereof include an inorganic base represented by glass, a metal base, an acrylic resin, a polycarbonate, and an organic base represented by polyethylene terephthalate. As a shape of a base material, plate shape, a film shape, etc. are mentioned. Moreover, one or more layers may be formed in the surface of a base material.

In coating the coating composition on the surface of the substrate, the method is not particularly limited, but, for example, brushing, spray coat, dipping (dip, dip coat), roll coat, flow coat, curtain coat, knife coat, Various conventional coating methods, such as a spin coat, a table coat, a sheet coat, a leaf coat, a die coat, and a bar coat, can be selected.

The film thickness of the cured coating film formed on the surface of a base material can be suitably selected according to a use use and an objective, and although it does not specifically limit, the range of 50-150 nm is preferable. Here, the product of the refractive index and the film thickness of the cured film is the optical film thickness, and the optical film thickness of the cured film needs to be set to 1/4? In order for the light having the wavelength? And in order for the light of wavelength (lambda) = 540 nm which is object of reflection prevention to become a minimum reflectance, when the refractive index of a cured film is 1.35, the film thickness of a cured film needs to be 100 nm (optical film thickness = 1.35 * 100 =). 135 ≒ 1/4 λ). In addition, when the refractive index of a cured film is 1.42, the film thickness of a cured film needs to be 95 nm (optical film thickness = 1.42x95 = 134.9 x 1/4 lambda). Thus, when optically designing as an anti-reflective film, the film thickness of a cured film has a preferable range of 50-150 nm.

Thus, when the coating material composition according to the present invention is used, a low refractive index cured film can be easily formed, and is suitable for antireflection applications. For example, when the refractive index of the base material is 1.60 or less, a cured film having a refractive index of 1.60 or more is formed on the surface of the base material, which is used as an intermediate layer, and the cured film is formed on the surface of the intermediate layer by the coating material composition according to the present invention. It is effective to form. If the cured film for forming an intermediate | middle layer can be formed using a well-known high refractive index material, and if the refractive index of this intermediate | middle layer is 1.60 or more, the difference of the refractive index with a cured coating will become large with the coating material composition by this invention. It is possible to obtain an antireflection base material having excellent antireflection performance. Moreover, in order to relieve coloring of the cured film of an antireflection base material, you may form an intermediate | middle layer by several layer from which refractive index differs. Examples of the antireflection use include an antireflection film, an outermost surface of a display, a side mirror of an automobile, a front glass, a side glass, an inner surface of a rear glass, other vehicle glass, building glass, and the like. have.

In addition, the film formed from the coating material composition according to the present invention also has high scratch resistance, antifouling property, chemical resistance, and crack resistance, and their performance is particularly high crack resistance at high temperature during film formation or after film formation. Even if it is exposed under the same conditions, it can be maintained satisfactorily. Therefore, even when a film is formed on a plastic substrate such as a plastic substrate, it is possible to form a film which hardly causes cracks during heating.

Hereinafter, an Example demonstrates this invention concretely. In addition, unless otherwise indicated, all "parts" represent a "mass part (weight part)", and "%" shows all the "mass% (weight%)" except the reflectance mentioned later. In addition, about the "solid content", the value converted into all oxides is shown.

(Example 1)

312.4 parts of methanol was added to 47.8 parts (0.08 mol) of the silane compound represented by the following formula (1), and 4.7 parts (0.02 mol) of γ-glycidoxypropyltrimethoxysilane as the epoxy group-containing organic compound, 0.1 N (0.1 mol) 36 parts of hydrochloric acid aqueous solution / L) was further added, and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 935 parts of propylene glycol monomethyl ethers were added and diluted to this solution, and the coating material composition of 3% of solid content was obtained.

(Example 2)

317.1 parts of methanol was added to 47.8 parts (0.08 mol) of the silane compound represented by said Formula (1), and 3.65 parts (0.01 mol) of siloxane oligomers represented by following formula (2) as an epoxy-group containing organic compound, 0.1N (0.1 mol / L) 36 parts of aqueous hydrochloric acid solution) was added, and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 1028 parts of propylene glycol monomethyl ethers were added to this solution and diluted to obtain a coating material composition having a solid content of 3%.

[Formula 10]

(Example 3)

315.3 parts of methanol was added to 47.8 parts (0.08 mol) of the silane compound represented by said Formula (1), and 3.5 parts (0.02 mol) of epoxy compounds represented by following formula (3) as an epoxy group containing organic compound, 0.1N (0.1 mol / L) 36 parts of aqueous hydrochloric acid solution) was added, and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 939.3 parts of propylene glycol monomethyl ethers were added to this solution and diluted to obtain a coating material composition having a solid content of 3%.

[Formula 11]

(Example 4)

As an alkyl fluoride-containing alkoxysilane, 109.2 parts of methanol was added to 21.8 parts (0.10 mol) of what was shown by following formula (4), 18 parts of 0.1N (0.1 mol / L) hydrochloric acid aqueous solution were added, and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 24 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 10 parts of this silicone resin and 90 parts of the silicone resin obtained in Example 2 were mixed, 233.3 parts of propylene glycol monomethyl ether was added and diluted to obtain a coating material composition having a solid content of 3%.

(Example 5)

37.3 parts of methanol was added to 20.8 parts (0.10 mol) of tetraethoxysilane, 1.8 parts of 0.1N (0.1 mol / L) hydrochloric acid aqueous solution was added, and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 10 parts of this silicone resin and 90 parts of the silicone resin obtained in Example 2 were mixed, and 233.3 parts of propylene glycol monomethyl ether was added and diluted to obtain a coating material composition having a solid content of 3%.

(Example 6)

As hollow silica fine particles, a hollow silica IPA (isopropanol) dispersion sol (solid content 20%, average primary particle diameter 60 nm, outer thickness about 10 nm, manufactured by Catalytic Co., Ltd.) was used, and this was diluted with methanol to 10% solid content to obtain a dispersion sol. 10 parts of this dispersion sol and 90 parts of the silicone resin obtained in Example 2 were mixed, 233.3 parts of propylene glycol monomethyl ether was added and diluted to obtain a coating material composition having a solid content of 3%.

(Comparative Example 1)

364.1 parts of methanol was added to 598 parts (0.10 mol) of the silane compounds shown in said Formula (1), 36 parts of 0.1N (0.1 mol / L) hydrochloric acid aqueous solution was added, and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 1073.1 parts of propylene glycol monomethyl ethers were added to this solution and diluted to obtain a coating material composition having a solid content of 3%.

(Comparative Example 2)

320.1 parts of methanol is added to 23.9 parts (0.04 mol) of the silane compound represented by said Formula (1), and 21.8 parts (0.06 mol) of siloxane oligomer shown by said Formula (2), and 0.1N (0.1 mol / L) hydrochloric acid aqueous solution 36 parts were further added and the mixed liquid which mixed this well was obtained. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 937.5 parts of propylene glycol monomethyl ethers were added to this solution and diluted to obtain a coating material composition having a solid content of 3%.

(Comparative Example 3)

50 parts of the silicone resin obtained in Example 4 and 50 parts of the silicone resin obtained in Example 2 were mixed, 233.3 parts of propylene glycol monomethyl ether was added and diluted to obtain a coating material composition having a solid content of 3%.

(Comparative Example 4)

50 parts of the silicone resin obtained in Example 5 and 50 parts of the silicone resin obtained in Example 2 were mixed, 233.3 parts of propylene glycol monomethyl ether was added and diluted to obtain a coating material composition having a solid content of 3%.

(Comparative Example 5)

341.7 parts of methanol was added to 41.8 parts (0.07 mol) of the silane compounds shown in said (1), and 10.9 parts (0.03 mol) of siloxane oligomers shown in said Formula (2), and 36 parts of 0.1N (0.1 mol / L) hydrochloric acid aqueous solution It further added and obtained the mixed liquid which mixed this well. This liquid mixture was stirred for 2 hours in a 25 degreeC thermostat, and the silicone resin of 10% of solid content was obtained. 1004.4 parts of propylene glycol monomethyl ether was added to this solution and diluted to obtain a coating material composition having a solid content of 3%.

(Furtherance)

The compounding ratio (weight%) in the coating material composition of each of the above Examples and Comparative Examples is shown in Table 1 below.

Table 1

a: content of the silane compound represented by Formula (A)

b: content of epoxy group-containing organic compound

(Film formation)

After leaving the coating material composition obtained by each Example and the comparative example for 1 hour, the acrylic plate (The Asahi Chemical Co., Ltd. make "Deragrass TMHA") which surface-washed previously with the UV-ozone washing machine (Excimer lamp "model HOO11" made by Ushio Electric Corporation) And a hard coat surface having a double-sided hard coat treatment and a hard coat refractive index of 1.52) were coated with a wire bar coater to form a film thickness of about 100 nm and treated at 100 ° C. for 30 minutes to obtain a cured coating film.

About this cured film, the evaluation test regarding minimum reflectance, abrasion resistance, fingerprint removal property, alkali resistance, and crack resistance was done as follows.

Minimum reflectance

The 5 degree relative minimum reflectance was measured using the spectrophotometer ("U-4100" by Hitachi Ltd.).

(Wear resistance)

Rub the surface of the cured film with abrasion tester (HEIDON-14DR manufactured by Rapid Science, Inc., steel wool # 0000, load 9.8 kPa (100 g / cm 2)), and observe the level of occurrence of damage occurring on the cured film. The mechanical strength was determined at.

A: No damage occurs.

B: Slight damage occurs.

C: Damage occurs.

D: Many damages occur (or peel).

(Fingerprint removal)

Fingerprints were affixed to the surface of the cured coating film, and the shape after wiping the fingerprint marks with OA Toreshi (manufactured by Toray Corporation) was observed, and fingerprint removability was determined by the following evaluation criteria.

A: It can be removed by several times.

B: It can be removed about ten times.

C: You can get rid of it if you wipe it hard.

D: It cannot be removed (marks are left).

(Alkali resistance)

In 25 degreeC 0.1N (0.1 mol / L) sodium hydroxide aqueous solution, the shape of the film after immersing a hardened film for 1 hour was observed, and alkali resistance was evaluated by the following evaluation criteria.

A: No change to the film.

B: Although the marks immersed in the film | membrane are seen, even if it rubs with a towel, it does not appear until peeling.

C: Peeling is not seen only by dipping, but peels off when rubbed with a towel.

D: It peels by immersion.

(Crack resistance)

The acrylic plate on which the film was formed was further baked at 110 degreeC for 30 minutes, then 120 degreeC for 30 minutes, and 130 degreeC for 30 minutes, and the crack resistance was evaluated at the baking temperature at which a crack generate | occur | produces in a film.

A: No crack occurred even at 130 ° C.

B: Crack generation at 130 ° C.

C: Crack generation at 120 ° C.

D: Crack generation at 110 ° C.

The above results are shown in Table 2 below.

TABLE 2

As in this result, in Examples 1 to 6, all of the evaluations were A or some of the evaluations were B, whereas in Comparative Examples 1 to 5, all the evaluations did not become B or more, and accordingly, In the coating composition, it was confirmed that high abrasion resistance, fingerprint removal property, alkali resistance and crack resistance can be realized at low reflection.

The present invention has a low refractive index and maintains high scratch resistance, antifouling property, chemical resistance, and crack resistance even when a film is formed on a plastic substrate such as a plastic substrate, when exposed to high temperature after film formation or after film formation. It is applicable to the coating material composition which can be used, and the coating goods which formed the film with this coating material composition.

According to the present invention, it is possible to form a film having high anti-reflective property, scratch resistance, antifouling property, chemical resistance and crack resistance, and to maintain these performances, especially when high crack resistance is exposed under high temperature. .

Claims (7)

The silane compound represented by the following general formula (A) and the epoxy group containing organic compound containing one or more epoxy groups in a molecule | numerator are contained, Content of the said silane compound is 60-97 weight% with respect to the resin component whole quantity, Content of an epoxy-group containing organic compound is 3 to 10 weight% with respect to resin component whole quantity, The coating material composition characterized by the above-mentioned.

[R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is a divalent organic group containing one or more fluorine atoms. X is a hydrolyzable group. m is an integer of 1 to 3.] The coating material according to claim 1, wherein the epoxy group-containing organic compound contains at least one compound selected from compounds represented by the following general formula (B) and compounds represented by the following general formula (C). Composition.

[R <^2> , R <^3> is a C1-C16 organic group and at least one contains an epoxy group. Z is a hydrolyzable group. n and p are integers of 0 to 2 and 1 ≦ n + p ≦ 3.] [Formula 1]

[R ⁴ to R ¹⁵ are organic groups, and at least one of them contains an epoxy group. q, r, s, t are integers from 0 to 12.] The coating material composition according to claim 1 or 2, wherein the epoxy group-containing organic compound contains two or more epoxy groups in a molecule. The coating material composition according to any one of claims 1 to 3, which contains an alkyl fluoride-containing alkoxy silane represented by the following general formula (D).

[R _f is a monovalent organic group containing at least one fluorine atom. X is a hydrolyzable group.] The coating material composition according to any one of claims 1 to 4, which contains a filler.  Content of the said epoxy group containing organic compound is 3 to 10 weight% with respect to the silane compound represented by the said General formula (A), The coating material composition in any one of Claims 1-5 characterized by the above-mentioned. The hardened | cured film of the coating material composition of any one of Claims 1-6 is formed in the surface of a base material, The coating goods characterized by the above-mentioned.